This invention is generally directed to toner and developer compositions, and more specifically, the present invention is directed to developer and toner compositions containing charge enhancing additives, which impart or assist in imparting a positive charge to the toner resin particles and enable toners with rapid admix characteristics. In one embodiment, there are provided in accordance with the present invention toner compositions comprised of resin particles, pigment particles, and teriary amine hydrogen ammoniumtriflate salts, including stearyl dimethyl hydrogen ammonium triflate charge enhancing additives, which additives can, it is believed, enable, for example, toners with rapid admix of less than about 60 seconds in some embodiments, substantially stable electrical properties, it is believed, and the like. The aforementioned toner compositions usually contain pigment particles comprised of, for example, carbon black, magnetites, or mixtures thereof, cyan, magenta, yellow, blue, green, red, or brown components, or mixtures thereof, thereby providing for the development and generation of black and/or colored images. The toner compositions of the present invention can possess excellent admix characteristics as indicated herein, and can, it is believed, in embodiments maintain their triboelectric charging characteristics for an extended number of imaging cycles exceeding, for example, 50,000 in some embodiments. The toner and developer compositions of the present invention can be selected for electrophotographic, especially xerographic, imaging and printing processes, including color processes.
Developer compositions with charge enhancing additives, which impart a positive charge to the toner resin, are known. Thus, for example, there is described in U.S. Pat. No. 3,893,935 the use of quaternary ammonium salts as charge control agents for electrostatic toner compositions. In this patent, there are disclosed quaternary ammonium compounds with four R substituents on the nitrogen atom, which substituents represent an aliphatic hydrocarbon group having 7 or less, and preferably about 3 to about 7 carbon atoms, including straight and branch chain aliphatic hydrocarbon atoms, and wherein X represents an anionic function including, according to this patent, a variety of conventional anionic moieties such as halides, phosphates, acetates, nitrates, benzoates, methylsulfates, perchloride, tetrafluoroborate, benzene sulfonate, and the like. U.S. Pat. No. 4,221,856 discloses electrophotographic toners containing resin compatible quaternary ammonium compounds in which at least two R radicals are hydrocarbons having from 8 to about 22 carbon atoms, and each other R is a hydrogen or hydrocarbon radical with from 1 to about 8 carbon atoms, and A is an anion, for example, sulfate, sulfonate, nitrate, borate, chlorate, and the halogens such as iodide, chloride and bromide, reference the Abstract of the Disclosure and column 3; a similar teaching is presented in U.S. Pat. No. 4,312,933, which is a division of U.S. Pat. No. 4,291,111; and similar teachings are presented in U.S. Pat. No. 4,291,112 wherein A is an anion including, for example, sulfate, sulfonate, nitrate, borate, chlorate, and the halogens. There are also described in U.S. Pat. No. 2,986,521 reversal developer compositions comprised of toner resin particles coated with finely divided colloidal silica. According to the disclosure of this patent, the development of electrostatic latent images on negatively charged surfaces is accomplished by applying a developer composition having a positively charged triboelectric relationship with respect to the colloidal silica.
In a patentability search report the following U.S. patents were reported: U.S. Pat. No. 4,562,135 which discloses dry positively charged colored toners with charge control agents of the formula X-A-C wherein X is a chromophore, A is a linking group and C is a triboelectric charge establishing group, see the Abstract and note column 4 wherein examples of C are provided; U.S. Pat. No. 4,556,624, which discloses toners with, for example, tetrafluoroborate charge additives, see for example column 4; and as background interest U.S. Pat. Nos. 4,560,635; 4,604,338 and 4,792,513.
There are illustrated in U.S. Pat. No. 4,338,390, the disclosure of which is totally incorporated herein by reference, developer compositions containing as charge enhancing additives organic sulfate and sulfonates, which additives can impart a positive charge to the toner composition. Further, there are disclosed in U.S. Pat. No. 4,298,672, the disclosure of which is totally incorporated herein by reference, positively charged toner compositions with resin particles and pigment particles, and as charge enhancing additives alkyl pyridinium compounds. Additionally, other documents disclosing positively charged toner compositions with charge control additives include U.S. Pat. Nos. 3,944,493; 4,007,293; 4,079,014 and 4,394,430.
The following representative prior art, all U.S. patents, is also mentioned: U.S. Pat. No. 4,812,381 relating to toners and developers with quaternary ammonium salts of the formula illustrated in column 3, the preparation thereof, see column 4, and also note the working Examples, see columns 7 and 8, wherein specific charge additives are reported; U.S. Pat. No. 4,675,118 which discloses certain quaternary salts as fabric softeners, see the Abstract of the Disclosure, and note column 1, for example, wherein X is as recited including OSO.sub.3 CH.sub.3 and halide; U.S. Pat. No. 4,752,550, the disclosure of which is totally incorporated herein by reference, directed to toners and developers with inner salts and mixtures thereof as charge additives, see for example column 4; U.S. Pat. No. reissue 32,883 (a reissue of U.S. Pat. No. 4,338,390), the disclosures of which are totally incorporated herein by reference, wherein toners with organic sulfonate and organic sulfate charge enhancing additives are illustrated, see columns 3, 4, and 5 to 10 for example; and U.S. Pat. No. 4,058,585 which discloses a process of extracting metals with organic solvent solutions of the salts of hydrogen ionic exchange agents, and quaternary ammonium compounds including bisulfates.
Processes for preparing quaternary ammonium salts by an ion exchange, or ion pair extraction method with soluble quaternary compounds is known, reference for example Phase Transfer Catalysis, Principles and Techniques, Academic Press, N.Y., 1978, especially page 76, C. M. Starks and C. Liotta, the disclosure of this textbook being totally incorporated herein by reference, and "Preparative Ion Pair Extraction", Apotekarsocieteten/Hassle, Lakemidel, pages 139 to 148, Sweden, 1974, the disclosure of which is totally incorporated herein by reference, which illustrates the preparation of certain bisulfates with water soluble ammonium salt reactants and a two-phase method wherein the product resides in the water phase.
Moreover, toner compositions with negative charge enhancing additives are known, reference for example U.S. Pat. Nos. 4,411,974 and 4,206,064, the disclosures of which are totally incorporated herein by reference. The '974 patent discloses negatively charged toner compositions comprised of resin particles, pigment particles, and as a charge enhancing additive ortho-halo phenyl carboxylic acids. Similarly, there are disclosed in the '064 patent toner compositions with chromium, cobalt, and nickel complexes of salicylic acid as negative charge enhancing additives.
There is illustrated in U.S. Pat. No. 4,404,271 a complex system for developing electrostatic images with a toner which contains a metal complex represented by the formula in column 2, for example, and wherein ME can be chromium, cobalt or iron. Additionally, other patents disclosing various metal containing azo dyestuff structures wherein the metal is chromium or cobalt include U.S. Pat. Nos. 2,891,939; 2,871,233; 2,891,938; 2,933,489; 4,053,462 and 4,314,937. Also, in U.S. Pat. No. 4,433,040 there are illustrated toner compositions with chromium and cobalt complexes of azo dyes as negative charge enhancing additives.
In Japanese Publication No. 54-145542 there is illustrated a negatively chargeable toner consisting of a resin, a colorant, and the charge control agent pyridoxine aliphatic acid ester; East German Patent Publication 218697 relates to liquid developers with charge control additives with structural units of Formulas (I), (II) and (III), and which contain olefinically polymerizable bonds; U.S. Pat. No. 3,850,642 relates to multilayer sensitive elements with ionizable salts, acids, esters, and surfactants as charge control agents; U.S. Pat. No. 2,970,802 illustrates a composition for the control of hypercholestermia, which composition consists of a nontoxic gelatin containing aluminum nicotinate; and U.S. Pat. No. 3,072,659 discloses a method of preparing aluminum salts of nicotinic acid.
Illustrated in U.S. Pat. No. 4,937,157, the disclosure of which is totally incorporated herein by reference, are toner compositions comprised of resin, pigment, or dye, and tetraalkyl, wherein alkyl, for example, contains from 1 to about 30 carbon atoms, ammonium bisulfate charge enhancing additives such as distearyl dimethyl ammonium bisulfate, tetramethyl ammonium bisulfate, tetraethyl ammonium bisulfate, tetrabutyl ammonium bisulfate, and preferably dimethyl dialkyl ammonium bisulfate compounds where the dialkyl radicals contain from about 10 to about 30 carbon atoms, and more preferably dialkyl radicals with from about 14 to about 22 carbon atoms, and the like. The aforementioned charge additives can be incorporated into the toner or may be present on the toner surface. Advantages of rapid admix, appropriate triboelectric characteristics, and the like are achieved with many of the aforementioned toners. Toners with charge additives are disclosed in the patents in copending applications recited in the aforementioned patent.
In copending application U.S. Ser. No. 547,001, the disclosure of which is totally incorporated herein by reference, titled Toner And Developer Compositions With Charge Enhancing Additives, with the listed inventor John L. Haack, there are illustrated, for example, toners with quaternary ammonium hydrogen bisulfate, or tetraalkyl ammonium sulfonate charge additives. One additive is of the formula R'.sub.2 R".sub.2 N+X- wherein R' is alkyl with from 1 to about 25 carbon atoms, R" is alkyl with from about 1 to about 8 carbon atoms, and X is an anion derived from a sulfonic acid. In the aforementioned copending application there are included reference to U.S. patents and copending applications that disclose toners with charge enhancing additives.
Although many charge enhancing additives are known, there continues to be a need for toners with additives, which toners can possess many of the advantages illustrated herein. Additionally, there is a need for positive charge enhancing additives which are useful for incorporation into black, and/or colored toner compositions. Moreover, there is a need for colored toner compositions containing certain charge enhancing additives. There is also a need for toner compositions with certain charge enhancing additives, which toners possess, it is believed, substantially acceptable stable triboelectric charging characteristics, and excellent admixing properties, especially for the addition of replenishment toner. Moreover, there continues to be a need for positively charged toner and developer compositions. Further, there is a need for toners with certain charge enhancing additives which can be easily and permanently dispersed into toner resin particles. There also is a need for positively charged black and colored toner compositions that are useful for incorporation into various imaging processes, inclusive of color xerography, as illustrated in U.S. Pat. No. 4,078,929, the disclosure of which is totally incorporated herein by reference; laser printers; and additionally a need for toner compositions useful in imaging apparatuses having incorporated therein layered photoresponsive imaging members, such as the members illustrated in U.S. Pat. Nos. 4,265,990 and 4,921,773, the disclosures of which are totally incorporated herein by reference. Also, there is a need for toner compositions which have the desired triboelectric charge level, for example, from about 10 to about 40 microcoulombs per gram, and preferably from about 10 to about 20 microcoulombs per gram, and in embodiments admix charging rates of from about 15 to about 60 seconds, and preferably from about 15 to about 30, as determined by the known charge spectrograph, reference for example U.S. Pat. No. 4,375,673, the disclosure of which is totally incorporated herein by reference. There is also a need for charge enhancing additives that have acceptable thermal stability and that will not decompose during toner processing at elevated temperatures.